Azo dyes



Patented May 17, 1938 AZO PATENT OFFICE DYES Henry Jordan and Swanie S. Rossander, Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, poration of Delaware Wilmington, DeL, a cor- No Drawing. Application July 22, 1937, Serial No. 155,042

6 Claims.

This invention relates to azo dyes. Particularly the invention relates to a method of applying compounds of the type described in Jordan et a1. application for Azo dyes, filed of even date herewith, Serial #155,041 to cellulose, within which term is meant the celluloses and regenerated cellulose.

It is an object of the invention to produce new dyes which have exceptional fastness to washing.

amino, tertiary amino, carboxy, and sulfonic acid, and aryl has a single nucleus from the group consisting of benzene and naphthalene, coupling it to, preferably, beta naphthol, or to other azo dyestufi coupling components.

The following examples illustrate but do not limit the invention. In these examples parts are by weight.

Example I l The objects lgif the inventionare accomplished, Five tenths t of cotton piece goods are generally dlazoflzmg the compound dyed in the usual manner, known to those skilled represented Y the in the art, with ten hundredths part of 3 4-amino-azobenzene-4-sodium-sulfonate+ l5 NHOG- 2-amino-benzidine (PAB)3 The dyed fabric is rinsed in cold water and put in 200 parts of water at 20 C. Add three tenths part of sodium nitrite and four tenths part of sulfuric acid. Stir minutes. Rinse with cold Nm water. Dissolve one tenth part of beta-naphthol NHOO 5 in 200 parts of water and one twentieth part of caustic soda. Stir the solution rapidly while Ary =N adding the above rinsed piece goods. Stir 15 I minutes. Rinse in cold water and dry. The 3 dyeing is a red orange shade. The probable formula of the dye on the fiber is:

-NHo0-C N= NaOaS -N== C N=N Hoin wh1ch X is one of a group consisting of hydro- E p I gen i Aryl-N=N 50 and Y is at least one of a group consisting of hydro- 55 gen, halogen, alkyl, alkoxy, hydroxy, secondary Five tenths part of cotton piece goods is dyed in the usual manner, known to those skilled in the art, with ten hundredths part of metanilic acid 1,6-Cleves acid- Z-amino-benzidine (PAB)2 The dyed fabric is rinsed in cold water and put in 200 parts of water at 20 C. Add three tenths part of sodium nitrite and four tenths part of sulfuric acid. Stir 15 minutes. Rinse with cold water. Dissolve one tenth part of beta-naphthol in 200 parts of water and one twentieth part of caustic soda. Stir the solution rapidly while S OaNaadding the above rinsed piece goods. Stir 15 minutes. Rinse in cold Water and dry. The dyeing is a brown shade. The probable formula of the dye on the fiber is:

zidine (PAB): when dyed on the fiber and developed with beta-naphthol, as in Example II above, gives a brown shade dyeing. The probable formula of the dyestuff on the fiber is:

N H c o N [I N v I Ezcample IV The dye amino G salt meta-toluidine meta toluidine 2-amino-benzidine (PAB): is dyed on the fiber per procedure of Example I or II above.

S OzNa Example III The dye amino G salt aniline-+2-amino-ben- OH OH It gives a yellow brown shade dyeing. The probable formula of the dye on the fiber is:

SO5Na CH (EH3 trating the invention:

tively little use.

Shade on Ex. Diazo component Coupling component cellulose SuJIanilic acid- 2-amino-5-hydroxy-naphtha- Beta-naphthol Red brown.

l eig-lgsulfonic acid 2-amino-benzidine s- 6 Sulfanilic acid- 2ramino-5-hydroxy-naphtha- 1-phenyl-3-methylfi-pyrazo- Yellow brown.

1(61;1Xil3-)Sl1lf0ni0 acid Z-amino-benzidine lone.

a. 7 Sulfanilic acid Z-amino-5-hydroxy-naphtha- Acetoaoet-anilide Do.

Iglfi-fulfonic acid Z-amino-benzidine 2. 8 Sulfanilic acid Z-amlno-5-hydroxy-naphtha- Mete-tolylene diamine Red brown. lg iggsulfonic acid 2-amino-benzidine a. 9 4-Amino-azobenzene-4-sodium-sulfonate 2- Beta-naphthol Red orange.

amino-benzidine (PAB)3. 10 Z-Naphthylamine-fi, S-disulfonio acid 2- do Bordeaux.

amino-benzidine (PAB)a. 11 2'Napht11y1amine-6, 8-disulfonicacid)cresid- Brown.

ine Z-amino-benzidine (PABh. 12 Metanilic acid 1, 6-Cleves acid 2- Do.

amino-benzidine (PAB);. 13 8-A1m'no-l-naphthol-3, fi-disulfonic acid -z Violet.

cresidine 2-amino-benzidine (PAB):4. 14 Sulfauilic acid 2-amino-benzidine (PABh. Brown. 15 Z-Naphthylamine-fi, 8-disulfonio acid ani- Do.

line 2-amino-benzidine (PABh. 16 Z-Naphthylamine-G, 8-disulfonic acid meta- Yellow brown.

toluidine meta-toluidine Zaminobenzidine (PAB)3.

In the above table (PAB) stands for (pata-amino-benzoyl).

used.

To be of greatest advantage the products of this invention should be produced on the fiber, other- SOzNa SOINE S OaNa We claim:

NHCO

wise their insolubility renders them of compara- As many apparently widely different embodimentsof this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

1. A compound represented by the formula:

3. A compound represented by the formula:

in which X is one of a group consisting of hydrogen,

A rylN=N and v Y Y A ry1N=NA ry1 N=N Y is at least one of a group consisting of hydrogen, halogen, alkyl, alkoxy, hydroxy, secondary amino, tertiary amino, carboxy, and sulfonic acid, and aryl has a single nucleus from the group consisting of benzene and naphthalene.

5. The process which comprises diazotizing a compound represente'dby the formula:

in which X is one of a group consisting of hydrogen,

Aryl-N=NArylN=N- Y is at least one of a group consisting of hydrogen, halogen, alkyl, alkoxy, hydroxy, secondary amino, tertiary amino, carboxy, and sulfonic acid,

7 and and aryl has a single nucleus from the group consisting of benzene and naphthalene, and coupling it with a compound from the group consisting of beta-naphthol, meta-tolylene-diamine, 1-phenyl-3-methyl-5-pyrazolone, and acetoacetaniline.

6. Cellulose dyed with the product produced by impregnating the cellulose with the compound represented by the formula:

NHa

NBC 0 in which X is one of a group consisting of hydrogen,

A ry1N==N- Y Y A ry1-N=NA 1ylN=N Y is at least one of a group consisting of hydrogen, halogen, alkyl, alkoxy, hydroxy, secondary amino, tertiary amino, carboxy, and sulfonic acid, and aryl has a single nucleus from the group consisting of benzene and naphthalene, diazotizing it on the fiber, and coupling it to one of a group of compounds consisting of beta-naphthol, metatolylene diamine, 1-pheny1-3-methyl-5-pyrazolone, and acetoacet-anilide.

HENRY JORDAN. SWANLE S. ROSSANDER. 

